Organotin-substituted s-triazines



United States Patent 12 Claims. (Cl. 260-242) ABSTRACT OF THE DISCLOSURE Organotin substituted s-triazines, which possess insecticidal, acaricidal, ovicidal, fungicidal, bactericidal, bacteriostatic, molluscacidal, algaecidal and herbicidal activity, are used also as anthelmintics. The production of the active components themselves, their combination with carriers in compositions, and their application as pesticides and especially as anthelmintics are described.

This application is a continuation-in-part of our c0- pending patent application Ser. No. 469,893, filed on July 6, 1965, now abandoned.

The present invention concerns now organotin substituted s-triazines, processes for the production of such compounds as well as biocidal agents which contain such compounds as active substances. It also concerns novel methods and compositions for combatting pests and microorganisms and for the protection of organic materials of all types from attack by pests and microorganisms.

The expression biocidal agent" in this application means those agents which contain biocidally active substances which have insecticidal, arcaricidal, ovicidal, fungicidal, anthelmintic, fungistatic, bactericidal, bacteriostatic, molluscacidal, algaecidal and/or herbicidal properties.

It has been found that organotin-substituted s-triazines of the formula wherein X, and X each represent sulphur, the imino or an alkylimino group or the direct bond,

X represents sulphur or the direct bond,

R R and R each represent an alkyl radical with 1 to 18 carbon atoms, an alkenyl radical with 3 to 18 carbon atoms, an alicyclic radical or an optionally substituted phenyl radical,

R, and R each represent hydrogen, an alkyl radical with 1 to 18 carbon atoms, an alkenyl radical with 3 to 18 carbon atoms, an alicyclic radical or an optionally substituted phenyl radical or together'with the corresponding bridging member X or X they represent the morpholine ring or, in cases in which X, or X is a direct bond, they also represent halogen, a halogenoalkyl group or the group wherein X ,'R R and R have the meanings given above, as well as their salts with inorganic and organic acids have excellent biocidal properties and are thus suitable as active ingredients for biocidal agents. The active substances and the agents produced therewith are suitable both for the protection of materials as well as of plants.

As alkyl or alkenyl radicals represented by R, to R in general Formula I are meant straight or branched chain radicals, e.g. the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, allyl, methallyl, butenyl and oleyl radicals. If R, to R represent an alicyclic radical, then a cycloalkyl or cycloalkenyl radical is to be understood such as the cyclopentyl and cyclohexyl radicals as well as the cyclopentenyl or cyclohexenyl radicals. As optionally substituted phenyl radicals represented by R, to R are meant phenyl radicals which can be monoor polysubstituted by halogen such as chlorine, fluorine, bromine, by nitro, by alkyl such as methyl, ethyl, propyl, isopropyl or by halogenoalkyl such as trifiuormethyl.

The new compounds of general Formula I are obtained according to the present invention by reacting a triazine derivative of the formula T I s 1 N X2-R4 (H) wherein X X R and R have the meanings given in Formula I and Q is the mercapto group or a halogen atom, with at least one equivalent of an organotin compound of the formula Y-S{I\R1 R, (III) wherein R R and R have the meanings given in Formula I and Y is a radical which can be split off as anion or cation, the reaction being performed in the presence of an inert gas for example, nitrogen and, if desired, in the presence of a solvent.

By a radical which can be split off as anion, symbolized by Y in Formula III, there is meant halogen, particularly chlorine, an alkoxy group such as the methoxy or ethoxy gorup, or a hydroxyl group; and an alkali metal ion such as the sodium, lithium or potassium ion is meant by a radical which can be split off as cation.

The reaction is preferably performed in the presence of a solvent which is inert to the reaction partners such as an aliphatic or aromatic hydrocarbon, e.g. benzene, toluene, xylene, an aliphatic or aromatic hydrocarbon, an ester, ketone or amide.

The new compounds of Formula I obtained by the process according to the invention are stable and colorless. They do not dissolve in water but are soluble in the usual organic solvents. They are used for the combatting of pests and microorganisms, for the protection of organic materials from attack by pests as herbicidal,

. unsubstituted phenyl or substituted phenyl, especially chlorophenyl or nitrophenyl, are highly active anthelmintics and useful, for instance, against liver fluke in domestic animals.

Particularly distinguished by superior activity among the compounds of ,this subclass are those of the formula wherein each of R R and R represents alkyl of from 3 to 8 carbon atoms, phenyl, chlorophenyl or benzyl, and each of R and R represents hydrogen or the grouping R, being preferably the latter.

The subclass of compounds falling under Formula I in which X, and X, represent nitrogen and X represents sulfur or a single direct bond are characterized, among their biocidal activities, by special usefulness as herbicides.

Among this second subclass of compounds falling under Formula I, there are distinguished by particularly good herbicidal activity those compounds which are of the following formula wherein Lower" used herein in connection with an aliphatic radical means that such radical has from 1 to 4 carbon atoms.

A third subclass of compounds falling under Formula I which is distinguished by good all-round biocidal activity, is formed by the compounds of the formula N Rg (lower alkyl) wherein each of R R and R represents alkyl of from 3 to 8 carbon atoms or phenyl, X, represents chlorine, bromine or the grouping (lower alkyl) and each of R and R represents hydrogen or lower alkyl. For the protection of organic materials, the active substances of Formula I are either worked into the material or the material is impregnated wtih solutions of active substance which, if desired, contain surface active substances. In this way, keratin materials such as skins, leather, casein and also materials based on cellulose such as wood, staple fiber, paper, cotton, also preparations such as paints and lacquers, glues such as printing thickeners made from starch or cellulose derivatives, oils of all types, paper treatment liquors, plastics and synthetic fibers of all types, plasticisers, cosmetic articles, such as ointments, powders, soaps, etc. can be protected from attack by pests, in particular eating and sucking insects, bacteria and fungi. Solvents used for the impregnation of materials are, in particular, organic solvents such as petroleum fractions, alcohols and ethylene glycol monoalkyl ethers. For the protection of materials, advantageously, solutions, dispersions or suspensions of the active substances are used which have a content of active ingredient of at least 0.01 g./liter.

The new compounds of Formula I can also be advantageously used as anthelmintic agents. Anthelmintic compositions containing compounds of Formula I are administered orally or abomasally in the form of solid or liquid preparations. Such agents can be adminstered as, for instance, solutions, emulsions, suspensions, powders, tablets, blouses and capsules.

The anthelmintic compositions containing compounds of Formula I can be administered to animals in single doses or in several doses. Depending on the kind of animal, the single doses may vary between 10 mg. and 300 mg. per kilogram bodyweight. In some cases it is possible by protracted administration to achieve a better effect or to decrease the total dosage. Y

The compounds of Formula I as well as the compositions containing them can also be added to feed or drenches whereby the concentration of the active compound should be between about 0.01 and 1%.

In order to prepare the above-mentioned forms of application, conventional solid carrier materials can be used such as, for instance, kaolin, talcum, bentonite, sodium chloride, calcium phosphate, carbohydrate, cellulose powder, ground cotton seed, carbowax, gelatine, or liquids such as water, if desired with addition of surfaceactive compounds, for instance ionogenic or non-ionogenic dispersion agents, oils and other solvents which are non-toxic to the animal organisms, such as alcohols.

If the anthelmintic compounds are to be applied in the form of feed concentrates, suitable carrier materials are, for'instance, enriched feed, grain for feeding, protein concentrates or solutions such as sugar solutions. Such concentrates may also contain other additives, for example vitamins, antibiotics, chemotherapeutics, bacteriostatics, fungistatics, coccidiostatics, hormones, compounds with anabolic activity or other growth-increasing compounds.

Another advantageous property of the compounds of Formula I is their molluscacidal'activity. Solutions containing the compounds of the present invention are especially useful molluscacidally-active agents.

For the combatting of pests which injure plants, stored goods and health, as well as for the control of weeds, the compounds of Formula I are applied in the form of dusts, sprinkling agents, granulates, wettable powders, pastes and emulsions as well as solutions. 4

The new compounds of Formula I can also be used for the disinfection of and for the protection of laundry from attack by microorganisms, as well as for use in dry cleaning agents. For this purpose, either washing or rinsing liquors are used which contain compounds of Formula I advantageously in concentrations of at least 0.01% or higher calculated on the weight of the liquor.

Examples of wash active substances contained in the washing liquors are anion active compounds such as aromatic sulfonic acids substituted by lipophilic groups, or their water soluble salts, e.g. the sodium salt of dodecyl benzene sulphonic acid or water soluble salts of sulphuric acid monoesters of higher molecular alcohols or their glycol ethers, e.g. soluble salts of dodecyl alco-. hol sulphate, or of dodecyl alcohol polyglycol ether sulphate, or alkali metal salts of higher fatty acids (soaps), in addition, non ionogenic wash active substances such as polyglycol' ethers of higher fatty alcohols, also polyglycol ethers of higher alkylated phenols as well as socalled amphoteric wash active substances such as the reaction products of alkali metal salts of lower halogen fattyacids with polyalkylene polyamines having lipophilic radicals, e.g. with lauryl diethylenetriamine. In addition the liquor can also contain the usual auxiliaries such as water soluble alkali perborates, alkali polyphosphates, alkali carbonates, alkali silicates, optical brighteners, plasticisers, salts having an acid reaction such as ammonium or zinc silicofluoride or certain organic acids such as oxalic acid, also finishers, eg those based on synthetic resin or starch.

The compounds of general Formula I according to the invention can also be used in combination with other antimicrobial substances, e.g. with halogenated diphenyl ureas, halogenated salicylanilides, halogenated hydroxydiphenyl ethers, halogenated benzoxazolones, polychlorohydroxy diphenyl methanes, halogendihydroxy-diphenyl sulphides, bactericidal 2-imino-imidazolidines or -tetrahydropyrimidines, biocidal quaternary compounds or with certain dithiocarbamic acid derivatives such as tetramethyl thiuram disulphide; The tn'azine organotin derivatives according to the invention are very active soaps, shampoos, or as additives to cosmetics such as ointments or creams.

The compounds of Formula I are excellently suitable as active ingredients in weed killers, particularly for the killing of weeds among cultivated plants as well as for hindering undesirable plant growth. By weeds are also meant here e.g. undesirable plants which have previously been cultivated. The organotintriazinesdefined above are also suitable as active substances for the influencing of plant growth in other ways, in particular for defoliation, e.g. of cotton plants, ripeness acceleration by early dehydration, e.g. of potato plants, also for the reduction of the amount of fruit formed, prolonging the harvesting period and time of storage.

It is an advantage of the biocidal compounds according to the invention that they show better stability and lower toxicity in concentrations of comparable biocidal activity, when compared with known biocidal organotin compounds.

The biocidal agents according to the invention are produced by known methods by'intimatel'y mixing and milling active substances of Formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. These agents can be used in the following forms Solid forms.Dusts, sprinkling agents, granulates such as coated granulateS, impregnated granulates and homogeneous granulates;

Water dispersible concentrates of active substances- Wettable powders, pastes, emulsions;

Liquid forms-Solutions.

To produce the solid forms for use, namely dusts, sprinkling agents and granulates, the active substances are mixed with solid carriers. Examples of such carriers are kaolin, talcum, bole, loes s, chalk, limestone, ground lime stone, ataclay, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and mag nesium sulphates, magnesium oxide, milled plastics fertilisers such as ammonium sulphate, ammonium phosphates, ammonium nitrate, urea etc., ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions,

active charcoal etc. each of'these carriers can be used alone or admixed with each other.

The particle size of the carriers is, for dusts advantageously up to about 100/L, for sprinkling agents from about /LO.2 mm. and for granulates from 0.2 mm.- 1 mm. (and larger).

As a general rule, the concentrations of active substances in the solid preparations is from 05-80%. To these agents can also be added commercially available additives which stabilise the active substance and/or nonionic, anionic and cationic surface active substances which improve the dispersibility of the active substances.

The concentrates of active substance which can be dispersed in water (wettable powders), pastes and emulsion concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface active substances and anti-foaming agents and, optionally, solvents. The concentration of active substance of these agents is 5-80%.

Wettable powders and pastes are obtained by mixing and milling the active substances with dispersing agents and pulverulent carriers in suitable mixers and milling machines until homogeneity is attained. Carriers are, for example, those mentioned in the paragraph dealing with solid forms for application. In some cases it is advantageous to use mixtures of carriers. Commercially available surface active substances'can also be used as dispersing agents.

. Examples of anti-foaming agents are: silicones, Antifoam A etc.

The active substances are so mixed, rmilled, sieved and strained with the additives mentioned above that the solid particle size in wettable powders is 2040 r and in pastes is not more than 3 To produce emulsion concentrates and pastes, liquid dispersing agents, organic solvents and water are used. Examples of solvents are: alcohols, benzene, xylenes toluene, dimethyl sulphoxide, dimethyl formamide and mineral oil fractions boiling between 120 and 350. The Solvents must be almost odorless, not phytotoxic, inert to the active substances and not easily inflammable.

In addition, the agents according .to the invention can be in the form of and be used as solutions. For this purpose the active substances of Formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Higher aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes alone or mixed with each other or with water or used as organic solvents. The solutions should contain the active substances in a I concentration from 1 to 20%.

rated into the agents according to the present invention,

in order to broaden the range of activity of the latter.

The following non-limitative examples serve to illustrate the various aspects of the present invention. Unless expressly stated otherwise, parts and percentages are given therein by weight and the temperatures are in degrees centigrade.

Example 1 30 parts of 2-mercapto-4,6-bis-amino-s-triazine are slurried in parts by volume of anhydrous toluene under an atmosphere of nitrogen and 59.6 parts of pure bis- (tri-n-butyl-tin)oxide are added. The reaction mixture is then refluxed for 6 hours while continuously introducing nitrogen. The Water formed in the reaction is quantitatively removed from the reaction mixture by azeotropic distillation. Undissolved substance is removed from the remaining reaction solution and then the solvent is distilled off from the solution in vacuo. The residue is oily and crystallizes on standing. Recrystallized from petroleum ether, the 2-(tri-n-butyl-stannylthio)-4,6-bisamino-s-triazine melts at 106-108. Because of its general biocidal and in particular insecticidal, fungicidal and bacteriostatic properties, the compound can be used for the preparation of insecticidal sprays and dusts on following the instructions given below.

By repeating Example 1, but using instead of the starting s-triazine an equimolar amount of Example 2.2-mercapto-4,6-bis-n-octadecylamino-s-triazine,

Example 3.-2-n1ercapto-4,6-bis-allyl-amino-s-triazine,

Example 4. 2-mercapto-4-octadecyl-amino-6 morpholino-s-triazine,

Example 5.--2-mercapto-4-hexylamino 6 cyclopentylamino-s-triazine,

Example 6.--2-anercapto-4-0ctylamino-6-cyclohexyl-amino-s-triazine,

Example 7.2-mercapto-4,6-bis-decenylamino-s-triazine,

there are obtained the 2-(tri-n-butyl-stannylthio)-bis-amino-s-triazines bearing the respective substituents at the amino nitrogen atoms in 4 and 6 positions.

Example 8 In the same way, on using 41.8 parts of anhydrous 2- mercapto-4,6-bis-ethylamino-s-triazine according to the process described in Example 1, Z-(tri-n-butyl-stannylthio)-4,6-bis ethylamino-s-triazine is obtained first as a yellowish oil which crystallizes on cooling. On recrystallizing from anhydrous ethanol, the substance is obtained as crystals which melt at 95-96". Because of its biocidal properties, which are similar to those of the final product of Example 1, it can be made up according to the methods given below into insetcicidal wettable powders, fumigants and emulsion concentrates.

Example 9 2-(tri-n-octyl-stannylthio)-4,6-bis-ethylamino-s-triazine is obtained by repeating Example 8, but using an equimolar amount of bis-(tri-n-octyl-tin)oxide in lieu of the bis-(tributyl-tin)oxide used in the said example.

Example 10 2-(tri-n-hexylstannylthio)-4,6-bis-ethylamino-s-triazine is obtained by repeating Example 8, but using an equimolar amount of bis-(tri-n-hexyl-tin)oxide in lieu of the oxide used in the said example.

Example 11 In the same way, on using 47.7 parts of anhydrous 2- mercapto-4,6-bis-isopropylamino-s-triazine according to the process described in Example 1, Z-(tri-n-butyl-stannylthio)-4,6-bis isopropylamino-s-triazine is obtained as a yellow oil; refraction index 11 215488. Because of its biocidal properties, the substance can be made up according to the instructions given below into insecticidal wettable powders and sprays or it can be used as disinfectant in soaps and detergents.

Example 12 2 (tri-n-propylstannyl-thio)-4,6-bis-isopropylamnio-striazine is obtained by repeating Example 11, but using an equimolar amount of bis-(tri-n-propyl-tin) oxide in lieu of the oxide used in Example 11.

This biocidal compound is particularly useful as a herbicide.

Example 13 In the same way, on using 44.8 parts of anhydrous 2 meccapto 4-ethylamino-6-isopropylamina-s-triazine according to the method described in Example 1, 2-(tri-nbutyl stannylthio) 4 isopropylamino-6-ethylamino-striazine is obtained as a yellow viscous oil which solidifies on cooling. Recrystallized from petroleum ether, the substance melts at 81. It has biocidal properties and can be made up into biocidal agents according to the instructions given geloW.

Example 14 On using 41.85 parts of anhydrous 2-mercapto-4- methylamino 6-isopropylamino-s-triazine, 2(tri-n-butylstannylthio) 4-isopropylamino-G-methylamino-s-triazine is obtained by the process described in Example 1 as a yellow oil. It forms crystals on cooling which, recrystallized from petroleum ether, melt at 7879. This substance also has biocidal properties and can be further worked up according to the instructions given below.

Example 15 2 (tri n propylstannyl-thio)-4-methylamino-6-isopropylamino-s-triazine is obtained by repeating Example 14, but using an equimolar amount of bis-(tri-n-propyltin)oxide in lieu of the oxide used in Example 14.

This biocidal compound is particularly useful as a herbicide.

Example 16 2 (triphenyl-stannylthio)-4-methylamino-6-isopropylamino-s-triazine is obtained by repeating Example 14, but using an equivalent amount of triphenyl-tin hydroxide in lieu of the amount of bis-(tri-n-butyl-tin)oxide used in the said example.

This biocidal compound is particularly useful as a herbicide.

Example 17 On using 18.6 parts of anhydrous trithiocyanuric acid and 89.4 parts of bis-(tri-n-butyl-tin)-oxide according to the method described in Example 1, 2,4,6-tris-(tri-n-butylstannylthio)-s-triazine is obtained as a clear yellowish oil 11 215521. The substance has biocidal properties and can be used in washing liquors for textile as a disinfectant for laundry.

Example 18 2,4,6 tris (tri n propylst'annyl thio) s triazine n =l.5655 is obtained by repeating Example 17, but using an equimolar amount of bis-(n-propyl-tin)oxide in lieu of the oxide used in Example 17.

This compound is a useful biocidal agent, and particularly a very good herbicide.

Example 19 2,4 bis (tri benzylstannyl thio) 6 mercaptos-triazine, M.P. 1l0112, is obtained by repeating Example 17 but using in lieu of the 89.4 parts of bis-(tri-nbut'y1-tin)-oxide, 81.8 parts of bis-(tribenzyl-tin)- hydroxide.

This compound is particularly useful as herbicide.

Example 20 A solution of 6 parts of sodium hydroxide in parts by volume of anhydrous ethanol are added dropwise at 56-60 to 12.10 parts of trithiocyanuric acid and 78 parts of triphenyl tin chloride suspended in 350 parts by volume of anhydrous ethanol and then the whole is refluxed for 5 hours. About two-thirds of the solvent are then distilled off in vacuo and the residue is poured into 1500 parts of water. The precipitate formed is filtered off under suction, washed with water and recrystallized from ethylene glycol monomethyl ether. The 2,4,6-tris-(triphenylstannyl-thio)- s-triazine melts at 200-202".

This compound is useful as a biocidal agent, particularly in paints and the like protective coatings and impregnation liquors applied on wood and other materials liable to be attacked by insects, fungi and for bacteria.

Furthermore this compound is particularly useful as an anthelmintic agent, e.g. against liver fluke in domestic animals.

Example 21 In a nitrogen atmosphere, 75.0 parts of triphenyl tin methoxylate are dissolved in 300 parts by volume of anhydrous toluene and mixed with 45.0 parts of pure 2-mercapto-4,'6-bis-isopropylamino-s-triazine. Then the reaction mixture is refluxed for 6 hours while nitrogen is being introduced continuously. The solvent is removed by vacuum distillationlfrom the reaction solution which has been freed from undissolved portions. The glassy pure 2 (triphenyl stanmyl thio) 4,6 bis isopropylaminos-triazine melts at 6870.

This compound is useful as a biocidal agent, especially as fungicide, e.g. as agricultural fungicide.

Example 22 11 parts of sodium metal are finely dispersed in 300 s-triazine is obtained analogously, starting from 2,4-dibromo-6methylamino-s-triazine.

NOTE. 0011 in the above table represents the phenyl radical.

parts of boiling anhydrous petroleum ether. A mixture of 716 parts of tributyl ti-n chloride and 520 parts of 2- chloro-4,6-bis-diethylamino-s-triazines added dropwise to this dispersion, and the whole is heated for 8 hours while a continuous nitrogen stream is introduced. The solvent is removed by vacuum distillation after the reaction solution has been freed from undissolved matter and the oily residue is fractionated in vacuo. 2-tri-n-butyl-stannyl-4,6 bis-diethylam ino-s-triazine passing over at 148152/ 0.005 torr. is a faintly yellowish oil having a refraction index of n =1.5137.

This compound is an effective biocidal agent and particularly useful, for instance, as a herbicide and fungicide.

Example 23 2 chloro 4 (triphenyl stannyl) 6 methylamino- S-triaZine is obtained by adding to 35.7 parts of triphenyl tin lithium dispersed in 300 parts of tetrahydrofuran at about -5, 1718 parts of 2,4-dichloro-6-methylamino-striazine dissolved in 200 parts of tetrahydrofunan, leaving the resulting mixture stand for 24 hours, separating lithium chloride formed by filtration and eliminating the solvent by distillation in vacuo.

This compound is an effective biocidal agent and particularly useful (as herbicide, bactericide and fungicide.

2 bromo 4 (triphenyl stannyl) 6 methylamino- In the following text the production and composition of typical forms for application of the biocidal agents according to the invention are described. Parts are given therein as parts by weight. Temperatures are given in degrees centigrade.

Example I 1 part of 2,4,6-tris-(tri-n-propylstannyl-thio)-s-triazine is intimately mixed with 99 parts of talcum. To produce a completely homogeneous mixture, this dust containing 1% of active substance is milled in a Kolloplex mill. This composition can be used for combatting cockroaches and ants.

Example II.Wettable powders (a) 25 parts of 2-(tri-npropylstannyl-thio)-4,6-bis-isopropylamino-s-triazine, 5 parts of a sulphonated hexadecyl glycol ether and 2.5 parts of a condensation product of sulphonated naphthalene and formaldehyde, and 67.5 parts of neutral sodium aluminium silicate are mixed and milled in a suitable apparatus. The 25% wettable powder obtained has good suspendability and is distinguished by little foam formation.

(b) 25 parts of 2-(tris-n-butylstannyl-thio) -4,6-bisethylamino-s-triazine, 50 parts of a condensation product of cetyl polyglycol ether and 8 mols of ethylene oxide, 2.5 parts of a condensation product of sulphonated naphthalene and formaldehyde, 25 parts of purified kieselguhr and 42.5 parts of kaolin are mixed and milled in suit- 11 able apparatus. The wettable powder has very good wettability.

Suspensions of any concentration desired can be produced from these wettable powders by dilution with water. The suspensions are used for the combatting of pests which attack stored goods in granaries and warehouses, etc.

Example lIL-Emulsion concentrates (a) 25 parts of Z-(tri-n-butylstannyl-thio) -4,6 -bisethylamino-s-triazine are dissolved in 55 parts of xylene and 20 parts of nonylphenyl polyglycol ether. An emulsifiable solution is obtained which can be diluted with water to any concentration desired.

(b) 25 parts of 2-(tri-n-butylstannyl-thio)-4,6-bis-dialkylamino-s-triazine are dissolved in 55 parts of petroleum distillate (boiling between 160-190"), 15 parts of polyglycol ether oleate and 5 parts of a combination emulsifying agent based on alkylaryl polyglycol ether and the calcium salt of an alkylaryl sulphonate. An emulsifiable solution is obtained which can be diluted to any concentration desired.

25 parts of 2,4,6-tris-(tri-n-propylstannyl-thio)-striazine are dissolved in 55 parts of petroleum distillate (boiling between 160190), 15 parts of polyglycol ether olcate and parts of a combination emulsifying agent based on alkylaryl polyglycol ether and the calcium salt of an alkylaryl sulphonate. A 25% emulsion concentrate is obtained which can be diluted with water to any concentration desired.

(d) parts of 2-(tri-phenylstannyl-thio)-4,6bis-is0- propylamino-s-triazine are mixed or dissolved with 20 parts of xylene, 20 parts of ethyl acetate, 30 parts of acetone and 20 parts of nonylphenyl polyethylene glycol ether. A 10% emulsion concentrate is obtained which can be diluted with water to any concentration desired. These emulsions are used for combatting pests which attack stored goods as well as midges and fiies in houses, farm outhouses, warehouses, etc.

Example lV.-Sprays (a) 2 parts of 2-(tri-n-butylstannyl-thio)-4,6-bis-isopropylamino-s-triazine are dissolved in 10 parts of xylene and 88 parts of petroleum.

(b) 2 parts of 2-(tri-n-butylstannyl-thio)-4-isopropylamino.-6-ethylamino-s-triazine and 3 parts of DDT active substance are dissolved in 95 parts of kerosene.

These solutions are sprayed under pressure. The solutions are used for combatting flies and midges in houses, warehouses and slaughter houses.

Example V.--Fumigants (a) 20 parts of 2,4,6-tris-(tri-n-propylstannyl-thio)-1, 3,5-triazine are mixed with 61 parts of sawdust which has previously been impregnated with 18.4 parts of potassium nitrate and the mixture is formed under pressure into tablets.

(b) 50 parts of Z-(tri-n-butylstannyl thio) 4,6 bisethylamino-s-triazine, 22 parts of sugar, 12 parts of potassium chlorate, 2.4 parts of potassium nitrate and 13.6 parts of sawdust are milled and intimately mixed. The fumigant mass is filled into tins and fitted with a wick or a fuse.

The fumigants serve to combat flies and midges in houses and warehouses.

In the following, the use of the active substances according to the invention for the protection of organic material such as textiles, plastics, wood, paper and oil and for the protection of plants is described.

(I) Use in the washing liquor for textiles The following active substances were tested as to their suitability for use for the protection of textiles: 2,4,6-tris-(tri-n-butylstannyl-thio)-s-triazine, 2,4,6-tris-(tri-n-propylstannyl-thio)-s-triazine,

12 2,4,6-tris-(triphenylstannyl-thio) -s-triazine, 2- (tri-n-butylstannyl-thio -4,6-diamino-s-triazine, 2,4-bis- (tribenzylstannyl-thio) -6-mercapto-s-triazine, 2-(tri-n-propylstannyl-thio) -4,6-bis-isopropylamino-s-triazlne, 2- (tri-n-butylstannyl-thio) -4,6-bis-isopropylamines-triazine, 2-(tri-n-butylstannyl-thio)-4-isopropylamino-6-methylamino-s-triazine, 2- tri-n-butylstannyl-thio) -4-isopropylamino-G-ethyl-amino-s-triazine, 2-(tri-n-butylstannyl-thio)-4,6-bis-ethylamino-s-triazine, Z-(triphenylstannyl-thio)-4,6-bis-isopropylamino-s-triazine.

Example A.The solution of 1 part of one of the above active substances in 20 parts of ethylene glycol monomethyl ether is added to a washing liquor which contains 1.5 g. of sodium soap per litre. Cotton cambric is introduced into this liquor, which contains 0.1% active substance per litre (liquor ratio 1:20), and the bath is heated to 40. The cotton is treated for 20 minutes at this temperature, then rinsed twice for 3 minutes at 40 with permutite water (liquor ratio 1:20), wrung out, dried and ironed.

Testing the action on bacteria-Circular samples each of 20 mm. diameter cut from the textile washed and finished according to Example A are laid on agar plates which have previously been injected with 24 hour old cultures of Staphylococcus aureus SG 511 or with about 5 day old cultures of Aspergillus niger. The agar plates are stored for 24 hours at 37.

Result.The circular samples treated with the organo tin triazine derivatives have neither Staphylococcus aureus SG 511 nor A spergillus niger and areas free from bacteria and fungi are formed on the agar around the samples.

Example B.-The amount of a solution of the above active substances in ethylene glycol monomethyl ether corresponding to 100 mg. of active substance per litre (1 part active substance in 20 parts of solvent) is added to equal parts of a washing liquor which contains 0.3 g. per litre of octylphenyl polyglycol ether and 1.7 g. of sodium polyphosphate per litre. Cuttings from cotton cambric are washed for 20 minutes at in each of the liquors so prepared, liquor ratio 1:20, then rinsed with permutite water in a liquor ratio 1:20, then squeezed out, dried and ironed.

The testing of the goods treated as to their resistance to attack by bacteria and fungi is performed'by the method described in Example A.

Result.The cotton treated as described above remained free from bacteria and fungi.

Example C.The solution of one of the above active substances in ethylene glycol monomethyl ether (1 part of active substance in 20 parts of solvent) is added to equal parts of a washing liquor containing 1.5 g. of sodium soap per'litre, so that the concentration of active substance is mg. per litre in each liquor. Wool muslin is washed at 40 in these preparations, liquor ratio 1:20. The textile is left for 20 minutes at this temperature, then rinsed twice for 3 minutes at 40 with permutite Water, liquor ratio 1:20, squeezed out and dried.

The testing of the goods treated as to their resistance t the growth of bacteria is performed by the method described in Example A.

Result.The goods treated according to Example C with the active substances given above remained free from Staphylococcus aureus SG 511 and Aspergillus nlger and areas free from bacteria and fungi are formed on the agar around the samples.

Example D.Nylon staple fibres are treated as described in Example C with liquors prepared as given therein.

The testing of the goods treated as to their resistance to the growth of bacteria and fungi is performed as described in Example A.

Result-Here also, the goods treated with the active substances given above were found to be free from Stalphylococcus aureus SG 511. The samples were surrounded by clear zones on the agar which were free from bacteria.

(II) Use in dry cleaning Example E.Samples of cotton cambric are washed with a dry cleaning agent containing mg. active substance per liter pure trichloroethylene. The samples are then squeezed between layers of filter paper and afterwards hung to dry in the air at room temperature. Testing of the treated cotton cuttings as to their bactericidal action according to Example A shows that the treated cotton fabric has been given a bactericidal and fungicidal finish.

In dry cleaning according to the process described above, the active substances given under I Use in washing liquors for textiles produced samples in which neither Staphylococcus aureus SG 511 nor Aspergillus niger could be found and areas free from bacteria and fungi are formed on the agar.

(III) Use in plastics Example F.200 parts of polyamide granulate (Grilon A G, Emser-Werke AG, Domat-Ems) and 1 part of active substance are mixed in a suitable mixer in a dry state for 1015 minutes and then formed in an injection-extrusion moulding machine at 260 into sheets of 55 x 36 mm. and 1 mm. thickness. Circular samples of 5 mm. diameter are cut from the polyamide sheets. The bactericidal activity is tested by placing the samples on nutrient agar which has previously been injected with 24- hour-old cultures of Staphylococcus aureus SG 511 or with S-day-old cultures of Aspergillus niger. The agar is then kept for 24 hours at 37. At the end of this time, clearly visible inhibition zones can be seen around the samples.

Example G.65 parts of polyvinyl chloride (Lonza G, Lonza AG, Basle), parts of dibutyl sebacate and 2 parts of dibutyl tin laurate are first mixed with 0.5 part of active substance, the mixture is then homogenised on a set of mixing rollers for 10 minutes at 160 and drawn out into films of 0.3 mm. thickness. As a compari son, films are produced in the same way but without the addition of the active substance. From the films produced, among which there is no visual ditference, circular samples of 20 mm. diameter are cut. These samples are placed in Petri dishes. The Petri dishes contain agar which has previously been injected With 24 hour old cultures of Staphylococcus aureus SG 511 or with 5 day old cultures of Aspergillus niger. The agar dishes are then kept for 24 hours at 37. At the end of this time, clear zones of inhibition can be seen.

Example H.0.8% active substance in the form of a solution in 6% sodium hydroxide stock solution is added to 200 g. of a viscose spinning solution containing 9.0% cellulose, the amount of active substance being calculated on weight of the cellulose. The stock solution is prepared by previously dissolving the active substance in 6% aqueous sodium hydroxide solution in a ratio of 1:12. This solution is intimately mixed with theviscose solution for 20 minutes. Air is then removed from the viscose solution. Viscose films are then produced in the known way which are afterwards washed, desulphurised and dried. Circular samples of 20 mm. diameter are cut from the viscose films and placed on nutrient agar which has previously been injected with 24 hour old cultures of Staphylococcus aureus SG 511 or 5 day old cultures of Aspergillus niger. The agar plates are kept for 24 hours at 37. At the end of this time clear zones of inhibition can be seen.

(IV) Use as preservative against blue stain The process used is taken from: H. Butin Holz als Rohund Werkstoff 19, 195 (1961).

Example J.The active substances are incorporated in a concentration of 1% into the preservative. 0.2 ml. of the preservative are applied to each block of pitch pine sap wood, the blocks being 4 x 5 cm. Alkyl resin lacquer is then painted over the preservative. 30 ml. of a fungus suspension were then applied to each Kolle dish containing the wood samples, each of which dishes were covered with 10 circles of filter paper of 1 0 cm. diameter. Pullularia pullulans was used as fungus. The Kolle dishes were kept for 6 weeks at 24 at relative humidity after which the blue stain on the wood samples was judged by measuring the depth of the zones free from blue stain.

Results: (given in millimeters) Depth of zone Depth of zone free from blueing free from blueing without treatwith treatment ment with active with active substance substance Active substance CO C Q (V) Use in paints based on dispersion dyestuffs Example K.A dispersion paint with a white pigment is used which is produced from a basis of copolymeric polyvinyl acetate as binder. It contains about 50% of solids. The active substance is dissolved in dimethyl forrnamide/ethylene glycol monomethyl ether (1:1) in a concentration of 5%. The stock solution is then added to the dispersion paint so that the ready-for-use dispersion paint contains 0.1% of active substance. 200 mg. of dispersion paint is evenly painted on Whatman No. 3 MM filter paper circles of 40 mm. diameter. The dry filter papers are then placed in Petri dishes containing 20 ml. of injected Sabouraud-Maltose Agar.

fungus on the circles of filter paper are measured.

Results: (given in millimeters) Test organisms Active substance in a concentration of 0.1%

2-(tri-n-butylstannyl-thio)4,fi di(ethylamino)-striazine Controls (VI) Use in cutting oil Example L.1 part of active substance dissolved in ethylene glycol monomethyl ether (1:1) is added to parts of emulsifiable cutting oil. This cutting oil concentrate is diluted with distilled Water so that in the emulsion a concentration of 0.1% of active substance is attained. 500 ml. of this emulsion are sterilised by heating for 15 minutes at in an autoclave; After testing the sterility, the emulsions are filled into glass vessels which can be aerated. A similar test is made with cutting oil not containing active substance. Air is bubbled through the emulsions for 7 days by means of a water jet pump. After 7 days, a sample of about 1 g. of the emulsion is taken and it is diluted with physiological sodium chloride solution in a ratio of 1:1 or 1:100. 0.5 ml. samples of this dilution are mixed with 15 ml. melted, sterile nutrient agar and the mixture is poured into Petri dishes. After storing the dishes for 48 hours at 37, the colonies are counted. The glass vessels, after the 1 g. sample has been taken therefrom, are injected with 2.5 ml. a mixture of filtered earth suspension (ear-th:water=l:2) and infected cutting oil emulsion (1:1). The test vessels are again aerated. After 24 hours and then after 7 days, again 1 g. of the emulsion is removed and diluted with physiological sodium chloride solution in a ratio of 1:1 or 1:100. 0.5 ml. of this dilution are mixed with 15 ml. of sterile, melted nutrient agar, the mixture is poured into Petri dishes and stored for 48 hours at 37. The colonies are then counted on the plates. The following results are obtained:

16 2,4,6 tris (tri n butylstannyl thio) striazine 24 Number of bacteria found after test 1asting- Concentration of emulsion 7 days not 1 day injected 7 days suspension 0.1% active substance injected with earth plus infected oil 2-(tri-n-butylstannyl-thio)4,0diamino-s- 2 0 100 10 10, 000 10, 000 triazine. 3 1 130 7 2,4,6-tris-(tri-n-butylstannyl-thio)-s- 2 0 160 4 10, 000 10, 000 triazine. 2 246 2,4,trtris-(tri-n-propylstannyl-thio)-s 0 0 10 1 10, 000 2, 100 triazine. 0 0 9 4 2, 400 2-(tri-n-butylstannyl-thi0)-4-isopropyl- 0 0 610 20 10, 000 1, 850 amino-(i-methylamino-s-triazine. 1 600 97 1, 600 Control without addition of active substance 100, 000 100, 000 100, 000 100, 000 100, 000 100, 000

N.B.Numbers =number of bacteria per plate containing a 0.5 ml. sample of the oil-emulsion dilution.

(VII) Use in plant protection-Proof of insecticidal action Example M: Contact poison-The insecticidal contact action is tested by dissolving 1 mg. of active substance in acetone, pouring the solution into Petri dishes and evaporating the solvent. After about 1 hour, the test insects given in the following table were placed in the Petri dishes. The values given in the table are the time [minutes or hours (h.)] in which all test insects (100%) are immobilised or in the dorsal position.

TABLE Test insects Bean beetles Bruchidius obtectus, hours Mosquitoes Aedes aegyptiz', minutes Active substance 2-(tri-n-butylstannyl-thio)-4,6bisethy1amino-s-triazine 2-(tri-n-butylstannyl-thio)4,6-

diamino-s-triazine 2,4,6-tris-(trim-butylstannylthio)-s-triazine 2-(tri-n-butylstannyl-thio) 4,6b1sisopropylamino-s-triaaine 2-(tri-n-butylstannyl-thio)-4 isopropylamino-G-ethylammostriazine 2-(tri-n-butylstannyl-thio)4- isopropylamino-fi-methylamino-striazine 1b. vrra: Wont- 4 Active substance: Potato beetle larvae, h.

Z-(tri-n-butylstannyl thio) 4,6 diamino -s triazine 5 2 (tri nbutylstannyl thio) 4,6 bis ethylamino-s-triazine 5 Mediterranean flour Active substance: moth larvae, percent 2- (tri-n butylstannyl thio) 4,6 diamino striazine 100 2,4,6-t ris-(tri-n-butylstannyl-thio)-s-triazine 100 2 (tri n butylstannyl thio) 4 isopropylamino-6-methylamino-s-triazine 100 Phytofungicidal action Example P: Spore germination test.The fungicidal activity of the active ingredients of the general Formula I was determined by a spore germination test with spores of the following types of fungi:

Alternarz'a tenuis Botrytis cinere'a Clasterosporium c. Coniothyrium dipl. Furarium. culmorum Mucor spec. Penicillium spec. Stemphylius cons.

A determined amount of a 1%, 0.1% and 0.01% acetone solution of active ingredient is placed on 2 glass slides of exactly the same size (26 X 76 mm.) under the same conditions. The solvent is evaporated off and a uniform coating of active ingredient which can be inoculated is obtained on the glass slides. The slides inoculated with fungi spores are then kept in dishes at room temperature in an atmosphere which is almost saturated with steam. After 2-3 and 4-6 days, the germinated spores are counted.

The concentrations of active ingredient are given in the following table which cause an inhibition of germination of at least in the following table shows an at least 90% inhibition of germination eiiected by the residue of 1 m1. of a 1% acetone solution of the active ingredient,

shows the same effect attained by the residue of a 0.1% acetone solution of the active ingredient,

shows an at least 90% inhibition of germination attained by the residue of 1 m1. of a 0.01% acetone solution of active ingredient,

Active substance Alt. ten. Botr. cm. Clast. c. Oom'oih. Fus. cuZm. Muc. Penic. SZd'mP/l.

dipl. spec. spec. cons.

2-(tri-n-butylstannyl-thio)-4,6-bis-ethylamino-stnazme--. Z-(tri-n-butyIStannyl-th1o)-4,6-dmmin0's-tr1az1ne 2,4,6-tris-(tri-n-butylstannyl-thio)-s-triazine 2-gtri-n-butylstannyl-thio)-4,G-bis-isopropylaminws ll'l. lllP 2-(tri n-butylstannylthio)-4-isopropylamino-6-ethylm o- 2-(tn-n-butylstannyLthw)-41sopr0pylam1no-6- et yl a azine 2-(tri-n-butylstannyl-thlo)-4,6-b1s-ethylaminostriazine 2-(triphenyl-stannyl-thio)-4,6-1sopropylam1n0-struazme. 2-(tri-n-butylstannyl-thio)-4-allylammo-6-methoxythy a m -s-trmz e 2-(tr1pheny-stannyl-tluo)-4-n-octadecy1amino-6- q ph lilwriazin 2-(tri-n-butylstannyl-thio)-4-n-propylam1 methoxy-n-propylamino-s-triazine Example Q.-Anthelmintic Activity Example S.Molluscacidal Activity Tests on mice suffering from Hymenolepis nana White mice were artificially infected with Hymenolepis nana. The anthelrnintic compounds of Formula I were administered to the mice through a stomach probe in the form of an emulsion. The active ingredients were administered once a day on one or several consecutive days. The animals were killed 8 days after the start of the test and then dissected.

The results were established by counting the number of tapeworms in the intestine. As control animals, untreated mice infected simultaneously and under the same conditions were used. The following table shows the Mortality Compound tested: in percent 2-(tri-n-butyl-stannyl-thio) 4 isopropylaminotest results. 6-6thYlilH1ll10-S-t1lElZll'l6 100 Dose in Adminis- H y'menolepis Toxicity Test compound mg. /kg. tered nana (mouse) percent per day (days) mortality 2,4,6-tris-(tri-phenyl-stannyl-thio) -s-triazine 50 3 Fully efiective 40 2- (triphenyl-stannyl-thio) -4-isopropylamino-6- methylamino-s-triazine 4 do 0 2-(triphenyl-stannyl-thio)-4-n-propylamino-6 allylamino-s-triazine 75 3 do 0 Z-(trip henyl-stannyl-thio)-4-allylamino-6-n1ethoxyethylamino-s-triazine 100 3 do 0 2-(tripheny1-stanny l-thio)-4-n-octadecy1-amino6- morpholino-s-triazine 200 3 0 Example R.--Tests on rats suffering from 1 .Fasciola hepatica (liver fluke) White rats were artificially infected with Fasciola hepatica. After the incubation period, the rats were tested for Fasciola hepatica by three faecal analyses, each independent of the other.

The infected rats were treated with an anthelrnintical- 1y active compound once a day on three consecutive days. The active ingredient was administered through a stomach probe in the form of a suspension. Three to five weeks after the application of the active substance a faecal analysis for eggs of Fasciola hepatica was carried out once a week. The test animals were killed at the end of the fifth week and examined for Fasciola hepatica still present. The test results are compiled in the following table.

2,4,6 tris (tri-n-propyl-stannyl-thio)-1,3,5-triazine 100 2 (tri-n-propyl stannyl thio) 4 isopropylamino-6-methylamino-s-triazine 100 Example T.Test on Australorbis glabratus Dose in Admini- Fasciola Toxicity Test compound mgJkg. stered hepatica percent per day (days) (rat) mortality 2- tri hen l-stcnn l-thio -4 fi-iso r0 ylamino-striaginei i 3 Fully effective" 0 2,4,6-tris-(triphenyl-stannyl-thio) -s-triazine 50 3 -do. 0 2-(triphenyl-stannyl-thio)-4-isopropylarmno-6- methylamino-s-triazine 50 3 do 0 2-(triphenyl-stannyl-thio)-4-n-butyla1mno-6 allylamino-s-triazine 50 3 -do 0 2-(triphenyl-stannyl-thio)-4- allylaminos-triazine 50 3 -do 0 2-(triphenyl-stannyl-thio) -6-methoxyetlliytllamipo-s-triztiiiiteii AYE? -2; 50 3 d0 0 2- tr en -stann*- i0 n-oc a co amino p y 3 y 3 do 0 morpholino-s-triazlne 19 then removed, washed and placed in clean water for 48 hours (aerated water was used for all tests and 100 ml. jars used as treatment containers). The values for the concentrations giving a mortality of 50% (LC 50) were obtained by plotting the dosage mortality data on logprobability paper.

Stabilisation of caseincontaining and starch-containing solutions Example U: Casein solutions-The compounds to be tested are dissolved in water or a solvent such as, for instance, ethyleneglycol ethylether in a proportion of 1:200 and added to a 10% casein solution consisting essentially of 10 g. of powdered casein, 88 g. of distilled water and 2 g. of concentrated ammonia (25%). The mixture is kept in an open glass vessel at 2328 C. The number of days which the mixture stays unchanged, i.e. does not change its odor, its viscosity, or its aspect, is taken as a measure for the activity of the composition.

The results are given in the following table:

Casein solution, p.p.m. of active substance in the substrate Compound tested Number of days 2-(triphenyLstannyl-thio)4,6-bis- Example V.Starch-containing solutions The compounds to be tested are dissolved in water or a solvent such as, for instance, ethyleneglycol ethylether in a proportion of 1:200. This solution is added to a 10% starch paste consisting essentially 10 g. of potato starch which was allowed to swell in 90 g. of distilled water at 60-65 C. The mixture is kept in a closed glass vessel at 23-28 C. The number of days during which the mixture stays unchanged, i.e. does not change its viscosity or its odor is taken as measurement for the activity of the preparation.

The results are given in the following table:

Starch solution, p.p.m. of active substance We claim: 1. A compound of the formula wherein each of R R and R represents alkyl of from 3 to 8 carbon atoms, phenyl, chlorophenyl or benzyl; each of R and R represents hydrogen or lower alkyl, each of R and R represents hydrogen, alkyl of not more than 18 carbon atoms, alkenyl of from 3 to carbon atoms, or cycloalkyl of from 5 to 6 carbon atoms,

or one or both of the pairs (R and R and (R and R taken together with the nitrogen atom to which 5 each pair is linked represent morpholino, and n reprewherein each of R R and R represents alkyl of from 3 to 8 carbon atoms, phenyl, chlorophenyl or benzyl; each of R and R represents hydrogen or lower alkyl, each of R and R represents hydrogen, alkyl of not more than 18 carbon atoms, alkenyl of from 3 to 10 carbon atoms, or cycloalkyl of from 5 to 6 carbon atoms, and R and R taken together with the nitrogen atom to which they are linked represent morpholino, and

n represents 0 or 1.

3. A compound as defined in claim 2 which is Z-(tri-npropylstannyl t-hio) 4 methyl amino 6 isopropylamino-s-triazine.

4. A compound as defined in claim 2 which is Z-(tri-npropylstannyl thio) 4,6 bis isopropyl amino s triazine.

5. A compound as defined in claim 2 which is 2-(triphenylstannyl thio) 4 methylamino 6 isopropylamino-s-triazine.

6. A compound as defined in claim 2 which is 2-(triphenylstannyl thio) 4,6 bis-isopropylamino-s-triazine.

7. A compound of the formula wherein each of R R and R represents alkyl of from 3 to 8 carbon atoms, phenyl, chlorophenyl or benzyl, and each of R and R represents hydrogen or the grouping /R1' -SI1R:'

8. A compound as defined in claim 7 which is 2,4,6- tris-(triphenylstannyl-thio)-s-triazine.

9. A compound as defined in claim 7 which is 2,4-bis- '(tri-benzylstannyl-thio)-6-mercapto-s-triazinc.

10. A compound of the formula wherein each of R R and R represents alkyl of from 3 to 8 carbon atoms or phenyl,

X; represents chlorine, bromine or the grouping (lower alkyl) 21 22 each of R and R represents hydrogen or lower alkyl. References Cited 11. A compound as defined in claim 10 which is Z-(tri- UNITED STATES PATENTS n-butyl-stannyl)-4,6-b1s-d1ethyl-arnmo-s-tnaz1ne. 2,766,234 10/1956 Gnmdmann et a]. n 26O 242 12. A compound as defined in claim 10 which is 2- chloro 4 (triphenyl stannyl) 6 methylamino s 5 HENRY JILES: P Emmmertriazine. R. T. BOND, Assistant Examiner. 

